Method for producing fluorinated compounds

ABSTRACT

The present invention relates to a process for the preparation of fluorinated compounds, to novel compounds containing fluorinated end groups, to the use thereof and to compositions comprising novel compounds containing fluorinated end groups.

The present invention relates to a process for the preparation offluorinated compounds, to novel compounds containing fluorinated endgroups, to the use thereof, and to compositions comprising novelcompounds containing fluorinated end groups.

Fluorine compounds are an important constituent in industrial processchemicals. Fluorine-containing compounds can be employed in a very widevariety of applications and contribute, for example, to improved wettingof surfaces. Thus, they are used, for example, as interface promoter oremulsifier or viscosity reducer in paints, coatings or adhesives or indirt-repellent coatings, for example in the textile industry.

Classical fluorine compounds are built up from long-chain,perfluorinated alkyl chains (C6-C8) and are regarded as potentiallybioaccumulative and toxic. Owing to their persistence and toxicity,these materials are problematic for users and the environment.

Shorter-chain fluorine building blocks are more favourable from theirecotoxicological profiles, but often exhibit poorer properties in theirareas of application.

Branched fluorosurfactants have also been known for some time. Owing tothe synthetic processes to date, the fluorine chains in branchedfluorine compounds always have the same chain length. There is thereforea need for novel fluorine-containing compounds and for processes for thepreparation of compounds which contain different fluorine-containinggroups.

The present invention relates to a process for the preparation offluorinated compounds of formula (I)

where firstly comounds of formula (II)

are prepared and these are then converted into the compouns of theformula (I) in a manner known per se, whereinRf is a fluorinated, linear or branched alkyl group, optionallycontaining further heteroatoms,R is a linear or branched alkyl or siloxane group, optionally containingheteroatoms, or a group Rf′, andRf′ is a fluorinated, linear or branched alkyl group, optionallycontaining further heteroatoms,to fluorinate compounds of the formulae (I′), (II) and (VI′), to usesthereof, and to compositions containing a compound of formula (VI′) anda vehicle which is suitable for the respective application andoptionally further specific active substances.

The present invention now makes it possible to prepare not only branchedfluorinated compounds containing identical fluorinated end groups, butalso branched fluorine compounds and fluorine-containing,functionalisable compounds having an asymmetrical structure.

The process according to claim 1 according to the invention enables thepreparation of branched, fluorine-containing compounds of the formula(I) which contain different fluorine-containing groups, for examplefluorine-containing alkyl chains having different chain lengths,starting from known, commercially available compounds. The novel processis also suitable for the preparation of “mixed-branched” compounds, i.e.compounds which contain both fluorine-containing and fluorine-freegroups. The process can equally also be utilised for the preparation ofbranched compounds containing identical fluorine-containing groups.

The branched alcohols of the formula (I) can then be converted into thecorresponding fluorinated surfactants, for example anionic or non-ionicsurfactants, or fluorinated acrylates or silanes.

The preparation of fluorinated materials having chains of differentlengths has a number of advantages. Thus, the properties with respect toCMC and surface-tension reduction can be manipulated in a furtherenvironment than is possible in the case of chains of equal length.

In solvent-containing paint systems, the combination of fluorinated andunfluorinated hydrocarbon surfactants is often recommended. Thecombination of fluorinated and unfluorinated chains in one molecule thusgives rise to the expectation of synergies that are not possible on useof pure fluorosurfactants.

The present invention relates firstly to a process according to claim 1for the preparation of fluorinated compounds of the formula (I)

where

-   -   Rf is a fluorinated, linear or branched alkyl group, optionally        containing further heteroatoms,    -   R is a linear or branched alkyl or siloxane group, optionally        containing heteroatoms, or a group Rf′, and    -   Rf′ is a fluorinated, linear or branched alkyl group, optionally        containing further heteroatoms.

In a first step of the process, a compound of the formula (II), in whichRf is a fluorinated, linear or branched alkyl group, optionallycontaining further heteroatoms, is prepared

and this is then converted into compounds of the formula (I) in a mannerknown per se.

The process according to the invention preferably comprises thefollowing steps, where Rf, R and Rf′ have the meanings given for theformulae (I) and (II):

-   -   a) reaction of compounds of the formula (III) with glycidol (IV)        to give compounds of the formula (II)

and

-   -   b) reaction of compounds of the formula (II) with alcohols of        the formula (V) to give compounds of the formula (I)

Rf is preferably a group of the formulaCF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—, where

-   -   a=0, 1, 2 or 3,    -   b=0 or 1,    -   c=0, 1, 2 or 3 and    -   d=0 or 1.

Rf′ is preferably a group of the formulaCF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—(CR¹R²)_(e)—(CR³R⁴)_(f)—O_(g)—,where

-   -   R¹, R², R³ and R⁴, independently of one another, are hydrogen or        an alkyl group,    -   a=0, 1, 2 or 3,    -   b=0 or 1,    -   c=0, 1, 2 or 3,    -   d=0 or 1,    -   e=0, 1, 2, 3 or 4,    -   f=0, 1, 2, 3 or 4 and    -   g=0 or 1.

The groups Rf and/or Rf′ can preferably be a fluorinated C1-C6-alkylgroup, particularly preferably a perfluorinated C1-C4-alkyl group, inparticular a perfluorinated C3-alkyl group.

The groups Rf and Rf′ are preferably not identical.

In a variant of the process, however, the groups Rf and Rf′ may also beidentical.

On use of siloxane-containing alcohols, the use of 1-propanol,3-[1,3,3,3 tetramethyl-1-[(trimethylsilypoxy]-1-disiloxanyl]- (Va) isparticularly suitable since this compound is commercially available andis employed in numerous surfactant applications.

Process steps a) and b) according to the invention are preferablycarried out as follows:

The conversion to formula (II) here is preferably carried out in aninert solvent (preferably an ether, for example dioxane or THF), a base(in particular carbonates or hydroxides of the alkali metals oralkaline-earth metals, preferably K₂CO₃ or NaOH), the correspondingfluoroolefin and glycidol.

Glycidol is preferably employed here in a stoichiometric or slightlysub-stoichiometric (1:1-1:0.85) ratio to the fluoroolefin. The lattersimplifies work-up and improves the yields. This reaction mixture isbrought to reaction in a pressure reactor, in particular at 80-140° C.,preferably 110° C., until the pressure drop flattens out (generally12-24 h). The work-up is carried out by washing by shaking with waterand drying of the organic phase. The yields are between 60-95%, based onthe glycidol. The partially fluorinated oxides can be purified well bydistillation under reduced pressure.

For the further reaction, epoxides and the corresponding alcohols arebrought to reaction with a catalyst system. Use is preferably made hereof a mixture of NaBH₄, Nal and 12 as described under U.S. Pat. No.5,608,116.

Alternatively, the reaction can be carried out with elemental Na orboron tri-fluoride diethyl ether. To this end, the alcohol is initiallyintroduced, the reagent is added under inert conditions and withcooling, and the epoxide is slowly metered in. When the addition iscomplete, the batch is slowly warmed to 80° C. and stirred vigorouslyfor several hours. Suitable alcohols for the additive ring opening here,besides fluorinated C1-C6-alcohols, are also purely aliphatic alcoholsor ether alcohols having a total chain length of C1-C20, preferablyC6-C14. However, other H-acidic compounds, such as, for example,siloxanes or thiols, are also possible.

The invention also relates to the intermediates of the process, i.e. thecompounds of the formula (II), where Rf is a fluorinated, linear orbranched alkyl group, optionally containing further heteroatoms,according to claim 7:

Rf is preferably a group of the formulaCF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—,

where a=0, 1, 2 or 3, b=0 or 1, c=0, 1, 2 or 3 and d=0 or 1.

Rf is particularly preferably a group of the formulaCF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(a)—where a=1 or 2, b=1, c=0 and d=0.

The present invention also relates to compounds of the formula (I′)according to claim 9.

where

-   -   Rf is a fluorinated, linear or branched alkyl group, optionally        containing further heteroatoms,    -   R is a linear or branched alkyl or siloxane group, optionally        containing heteroatoms, or a group Rf′,    -   Rf′ is a fluorinated, linear or branched alkyl group, optionally        containing further heteroatoms,    -   and, if R is a group Rf′, Rf and Rf′ are different.

Preference is given to compounds of the formula (I′) in which Rf is agroup of the formulaCF₃—(CF₂)₀₋₃— or CF₃—(CF₂)₀₋₃—O—.

Rf is particularly preferably a group of the formulaCF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—where a=1 or 2, b=1, c=0 and d=0.

The group R can preferably be a C1-C20 alkyl group, in particular aC6-C14 alkyl group, or a siloxane group.

Rf′ is preferably a group of the formulaCF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—(CR¹R²)_(e)—(CR³R⁴)_(f)—O_(g)—where

-   -   R¹, R², R³ and R⁴, independently of one another, are hydrogen or        an alkyl group,    -   a=0, 1, 2 or 3,    -   b=0 or 1, in particular 1    -   c=0, 1, 2 or 3, in particular 0    -   d=0 or 1, in particular 0    -   e=0, 1, 2, 3 or 4, in particular 0 and 1    -   f=0, 1, 2, 3 or 4, in particular 0, and    -   g=0 or 1, in particular 0.

Particular preference is given to compounds of the formula (I′) in whichRf and Rf′ have the preferred meanings.

R is furthermore preferably CH₂—CH₂—Si (CH₃)[O—Si(CH₃)₃]₂

The invention furthermore relates to the use of compounds of the formula(I) for the preparation of compounds of the formula (VI):

where

-   -   Rf is a fluorinated, linear or branched alkyl group, optionally        containing further heteroatoms,    -   R is a linear or branched alkyl or siloxane group, optionally        containing heteroatoms, or a group Rf′,    -   Rf′ is a fluorinated, linear or branched alkyl group, optionally        containing further heteroatoms,    -   L is a single bond or a divalent organic group and    -   X is a cationic, non-ionic, amphoteric or anionic group.

The groups Rf, R, and Rf′ preferably have the meanings given for theformula (I), in particular the preferred meanings.

The introduction of the hydrophilic, anionic, cationic, reactive orpolymerisable end group is possible for the person skilled in the art byknown methods.

An example of non-ionic surfactants which should be mentioned here wouldbe polyethylene glycol or polypropylene glycol or copolymers thereof,which can be prepared from the corresponding monomeric epoxides. It isadvantageous in the case of these compounds that the so-called HLB valueof the compound can be set via the chain length.

Reaction of the alcohol with glycidyltrimethylammonium chloride givescationic surfactants.

A simple method for the preparation of anionic surfactants is thepreparation of so-called phosphoric acid esters. In this method, thefluorinated alcohol is reacted with P₂O₅ or POCl₃ and neutralised usinga base. A further possibility for the preparation of anionic surfactantsis reaction of the alcohol with SO₃ or concentrated sulfuric acid togive so-called sulfates.

Polymerisable groups which may be mentioned in particular are the(meth)-acrylates, which can be obtained from the corresponding acidchlorides or anhydrides.

The invention furthermore also relates to the corresponding fluorinatedsurfactants and fluorinated compounds containing anchor groups, forexample fluorinated acrylates, which can be prepared from the branchedalcohols of the formula (I′). These compounds are represented by theformula (VI′), where X stands for a hydrophilic group, preferably ananionic, cationic, non-ionic group or an anchor group, preferably anethylenically unsaturated group, in particular an acrylate ormethacrylate group, an alkoxysilane group or a halosilane group, and Lis a single bond or a divalent organic group.

The present invention thus relates to compounds of the formula (VI′)according to claim 14:

where

-   -   Rf is a fluorinated, linear or branched alkyl group, optionally        containing further heteroatoms,    -   R is a linear or branched alkyl group, optionally containing        heteroatoms, or a group Rf′,    -   Rf′ is a fluorinated, linear or branched alkyl group, optionally        containing further heteroatoms,    -   L is a single bond or a divalent organic group and    -   X is a cationic, non-ionic, amphoteric or anionic group    -   and, if R is a group Rf′, Rf and Rf′ are different.

The compounds of the formula (VI′) preferably contain a group Rf havingthe formula CF₃—(CF₂)₀₋₃— or CF₃—(CF₂)₀₋₃—O—.

The group R can preferably be a C1-C20 alkyl group, in particular aC6-C14 alkyl group.

Rf′ is preferably a group of the formulaCF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—(CR¹R²)_(e)—(CR³R⁴)_(f)—O_(g)—where

-   -   R¹, R², R³ and R⁴, independently of one another, are hydrogen or        an alkyl group,    -   a=0, 1, 2 or 3    -   b=0 or 1, in particular 1    -   c=0, 1, 2 or 3, in particular 0    -   d=0 or 1, in particular 0    -   e=0, 1, 2, 3 or 4, in particular 0 and 1    -   f=0, 1, 2, 3 or 4, in particular 0, and    -   g=0 or 1, in particular 0.

Particular preference is given to compounds of the formula (VI′) inwhich Rf and Rf′ have the preferred meanings.

A preferred anionic group X can be selected from —COO⁻, —SO₃ ⁻, —OSO₃ ⁻,—PO₃ ²⁻, —OPO₃ ²⁻, —(OCH₂CH₂)_(s)—O—(CH₂)_(t)—COO⁻,—(OCH₂CH₂)_(s)—O—(CH₂)_(t)—SO₃ ⁻, —(OCH₂CH₂)_(s)—O—(CH₂)_(t)—OSO₃ ⁻,—(OCH₂CH₂)_(s)—O—(CH₂)_(t)—PO₃ ²⁻, —(OCH₂CH₂)_(s)—O—(CH₂)_(t)—OPO₃ ²⁻

where s stands for an integer from the range from 1 to 1000 and t standsfor an integer selected from 1, 2, 3 or 4.

The preferred anionic groups here include, in particular, —COO⁻, —SO₃ ⁻,—OSO₃ ⁻, —PO₃ ²⁻, —OPO₃ ²⁻, the sub-formula A, and—(OCH₂CH₂)_(s)—O—(CH₂)_(t)—COO⁻, —(OCH₂CH₂)_(s)—O—(CH₂)_(t)—SO₃ ⁻ and—(OCH₂CH₂)_(s)—O—(CH₂)_(t)—OSO₃ ⁻, where each one of these groups per semay be preferred. X can also stand for the corresponding acids.

The very particularly preferred anionic groups here include —SO₃ ⁻,—OSO₃ ⁻, —COO⁻, —PO₃ ²⁻, or OPO₃ ²⁻. In particular, a sulfonate group—SO₃ ⁻ is preferred. Preferred counterion for anionic groups X is amonovalent cation, in particular H⁺, an alkali-metal cation or NR₄ ⁺,where R=H or C1-C6-alkyl and all R may be identical or different.Especial preference is given to H⁺, Na⁺, K⁺, Li⁺ and NH₄ ⁺, particularlypreferably Na⁺.

A preferred cationic group X can be selected from —NR¹R²R³+Z⁻,—PR¹R²R³+Z⁻,

-   -   where R stands for H or C1-4-alkyl in any desired position,    -   Z⁻ stands for Cl⁻, Br⁻, I⁻, CH₃SO₃ ⁻, CF₃SO₃ ⁻, CH₃PhSO₃ ⁻,        PhSO₃ ⁻    -   R¹, R² and R³ each, independently of one another, stand for H,        C₁₋₃₀-alkyl, Ar or CH₂Ar and    -   Ar stands for an unsubstituted or mono- or polysubstituted        aromatic ring or condensed ring systems having 6 to 18 C atoms,        in which, in addition, one or two CH groups may be replaced by        N.

The preferred cationic groups here include, in particular, —NR¹R²R³+Z⁻and

where each one of these groups per se may be preferred.

A preferred non-ionic group can be selected from: linear or branchedalkyl, where one or more non-adjacent C atoms have been replaced by O,S, and/or N,

—OH, —SH, —O-(glycoside)_(o′), —S-(glycoside)_(o′), —OCH₂—CHOH—CH₂—OH,—O CH₂Ar(—NCO)_(p′), —OAr(—NCO)_(p′), amine oxide,

-   -   u stands for an integer from the range from 1 to 6, preferably 1        to 4    -   o′ stands for an integer from the range from 1 to 10,    -   p′ stands for 1 or 2,    -   Ar stands for an unsubstituted, mono- or polysubstituted        aromatic ring or condensed ring systems having 6 to 18 C atoms,        in which, in addition, one or two CH groups may be replaced by        C═O and,    -   glycoside stands for an etherified carbohydrate, preferably for        a mono-, di-, tri- or oligoglucoside.

The preferred non-ionic groups X here include, in particular, linear orbranched alkyl, where one or more non-adjacent C atoms have beenreplaced by O, S and/or N, —OH and —O-(glycoside)_(o′).

If X=alkyl, where one or more non-adjacent C atoms have been replaced byO, S, and/or N, it is then preferably equal to R⁴-(B-A)_(m) ⁻ -, whereR⁴=H or C1-4-alkyl, in particular H or CH₃, A=linear or branchedalkylene, preferably having 1 to 10 carbon atoms, in particular having 1to 4 carbon atoms, B═O or S, preferably O, and m″=an integer preferablyfrom the range from 1 to 100, particularly preferably 1 to 30.

The non-ionic group X is particularly preferably the groupR⁴—(O—CH₂CHR⁵)_(m) ⁻ -, where m″=an integer from the range from 1 to100, preferably 1 to 30, in particular also 1-25, and R⁴ and R⁵=H orC1-4-alkyl, in particular H or CH₃. R⁴—(B-A)_(m″) ⁻ is particularlypreferably a polyethylene glycol or polypropylene glycol unit.

The non-ionic group X is particularly preferably the group—CH(OH)—CH₂—NH-sach, where sach=various sugars and the group—Y—(CH₂—CH₂—O)_(v)—R⁴ where Y=S, O or NH, preferably O, R⁴=H or alkyl,preferably H or CH₃, and v=1-100, preferably 1-30, in particular also1-25.

A preferred amphoteric group X can be selected from the functionalgroups of the acetyldiamines, the N-alkylamino acids, theN-alkylaminosulfonic acids, the betaines, the sulfobetaines, orcorresponding derivatives, in particular selected from the followinggroups, where M stands for H or an alkali-metal ion, preferably Li⁺, Na⁺or K⁺:

Particularly preferred compounds according to the invention are thosewhich contain, as hydrophilic group X, one of the preferred anionicgroups, the preferred non-ionic groups or the preferred zwitterionicgroups. Particular preference is given to compounds which contain thegroups —SO₃ ⁻, —OSO₃ ⁻, —COO⁻, —PO₃ ²⁻ or OPO₃ ²⁻, polyethylene glycolsor polypropylene glycols, —CH(OH)—CH₂—NH-sach, Y—(CH₂—CH₂—O)_(v)—R⁴,betaines, or sulfobetaines. Preferred counterions here are H⁺, Na⁺, K⁺and NH₄ ⁺, in particular Na⁺. Particular preference is given to: —SO₃,—COO⁻, polyethylene glycols or polypropylene glycols, sulfobetaines, thegroup —CH(OH)—CH₂—NH-sach and the group Y—(CH₂—CH₂—O)_(v)—R⁴. sachhere=various sugars and Y═S, O or NH, preferably O, R⁴=H or alkyl,preferably H or CH₃, and v=1-100, preferably 1-30, in particular also1-25. Compounds where X=—SO₃ ⁻ may also be particularly advantageous.

Advantages of the compounds of the formula (VI′) according to theinvention may be, in particular:

-   -   a surface activity which is equal or superior to that of        conventional hydrocarbon surfactants with respect to efficiency        and/or effectiveness,    -   biological and/or abiotic degradability of the substances        without the formation of persistent perfluorinated degradation        products, such as PFOA (perfluorooctanoic acid) or PFOS        (perfluorooctanesulfonate),    -   can be prepared by simple processes,    -   weak foaming action and/or low foam stabilisation,    -   good processability in formulations and/or    -   storage stability.

The compounds according to the invention can preferably have aparticular surface activity. The compounds of the formula (VI′)according to the invention, in particular the preferred compounds, mayin addition have improved environmental properties, since they do notdegrade chemically or biologically to give long-chain PFCAs or PFASs.

The compounds according to the invention can preferably be convertedcompletely into mineralisable/regeneratable compounds by correspondingenvironmental influences.

The invention likewise relates to the use of compounds of the formula(VI′) and compositions comprising compounds of the formula (VI′).

The compounds of formula (VI′) can preferably be used as surface-activeagents, preferably as surfactant, hydrophobicising agent, interfacepromoter, viscosity reducer, foam stabiliser or emulsifier. The presentinvention therefore furthermore relates to the use of the compoundsaccording to the invention and the preferred embodiments described aboveas surface-active agents, for example for improving the flow behaviourand the wetting capacity of coating formulations in particular of thesaid particularly preferred compounds.

Besides the compounds of the formula (VI′), the mixtures according tothe invention may also comprise solvents, additives, assistants andfillers as well as unfluorinated surfactants. Mention may be made by wayof example of silicone particles, plasticisers and surface-modifiedpigments.

Preferred areas of use are, for example, the use of thefluorosurfactants of the formula (VI′) according to the invention asadditives in preparations for surface coating, such as paints, coatings,protective paints, special coatings in electronic or semiconductorapplications (for example photoresists, top antireflective coatings,bottom antireflective coatings) or in optical applications (for examplephotographic coatings, coatings of optical elements), in agrochemicals,in polishes and waxes, for example for furniture, flooring andautomobiles, in particular in floor polishes, in fire-extinguishingcompositions, lubricants, in photolithographic processes, in particularin immersion photolithography processes, for example in developersolutions, rinse solutions, immersion oils and/or in the photoresiststhemselves, especially for the production of printed circuits or inadditive preparations for addition to corresponding preparations.

In addition, the compounds which can be used in accordance with theinvention as surfactant are suitable for washing and cleaningapplications, and for use as additives/surfactants in cosmetic products,such as, for example, hair- and body-care products (for exampleshampoos, hair rinses and hair conditioners), foam baths, creams orlotions having one or more of the following functions: emulsifiers,wetting agents, foaming agents, glidants, antistatic, agents forincreasing the resistance to skin greases.

For use, the fluorosurfactants according to the invention are usuallyintroduced into correspondingly designed preparations. Usual useconcentrations are 0.01-1.0% by weight of the surfactants according tothe invention, based on the preparation as a whole.

The present invention likewise relates to corresponding compositionscomprising the fluorosurfactants according to the invention. Suchcompositions preferably comprise a vehicle which is suitable for therespective application, and optionally further active substances and/oroptionally assistants. Preferred compositions are paint and coatingpreparations, fire-extinguishing compositions, lubricants, washing andcleaning compositions and deicers or developer solutions, rinsesolutions, immersion oils and photo-resists for photolithographicprocesses, in particular for immersion photolithography processes and inparticular for the production of printed circuits, agrochemicals, floorpolishes, cosmetic products or hydrophobicising compositions for textilefinishing or glass treatment. Preferred compositions here are paint andcoating preparations and printing inks.

In addition, the present invention also relates to water-based coatingformulations which comprise the fluorosurfactants according to theinvention, alone or in a mixture with additives. Coating formulationsbased on the following synthetic film formers are preferably used:polycondensation resins, such as alkyd resins, saturated/unsaturatedpolyesters, polyamides/imides, silicone resins; phenolic resins; urearesins and melamine resins, polyaddition resins, such as polyurethanesand epoxy resins, polymerisation resins, such as polyolefins, polyvinylcompounds and polyacrylates.

In addition, the fluorosurfactants according to the invention are alsosuitable for use in coatings based on natural products and modifiednatural products. Preference is given to coatings based on oils,polysaccharides, such as starch and cellulose, and also based on naturalresins, such as cyclic oligoterpenes, polyterpenes and/or shellac.

The fluorosurfactants according to the invention can be used both inphysically curing (thermoplastics) and also in crosslinking (elastomersand thermosets) aqueous coating systems. The fluorosurfactants accordingto the invention preferably improve the flow and wetting properties ofthe coating systems.

The present invention relates to all uses mentioned here offluorosurfactants to be employed in accordance with the invention, inparticular of the preferred compounds. The respective use offluorosurfactants for the said purposes is known to the person skilledin the art, meaning that the use of the fluorosurfactants to be employedin accordance with the invention presents no problems.

The following examples explain the present invention in greater detailwithout restricting the scope of protection.

EXAMPLES

Abbreviations

-   -   PPVE perfluoropropyl vinyl ether    -   MTBE tert-butyl methyl ether    -   PPOL-1 2,2,3-trifluoro-3-heptafluoropropyloxypropan-1-ol        Determination of the Static Surface Tension

The static surface tensions γ of aqueous surfactant solutions havingvarious concentrations c (grams per litre) are determined.

-   -   Instrument: Dataphysics tensiometer (model DCAT 11)    -   Temperature of the measurement solutions: 20°±0.2° C.    -   Measurement method employed: measurement of the surface tension        using the Wilhelmy plate method in accordance with DIN EN 14370.    -   Plate: platinum, length=19.9 mm

In the plate method, the surface or interfacial tension of thesurfactant solution is calculated from the force acting on the wettedlength of a plate, in accordance with the following formula:

$\gamma = {\frac{F}{{L \cdot \cos}\;\theta} = \frac{F}{L}}$

γ=interfacial or surface tension; F=force acting on the balance;L=wetted length (19.9 mm); θ=contact angle. The plate consists ofroughened platinum and is thus optimally wetted so that the contactangle θ is close to 0°. The term cos θ therefore reaches approximatelythe value 1, so that only the measured force and the length of the platehave to be taken into account.

Example 1

21.78 g of glycidol, 93.86 g of PPVE, 12.19 g of potassium carbonate;130 ml of dioxane

The starting materials are combined in a 300 ml pressure reactor andstirred at 110 C. for 24 h. At the beginning of the reaction, a pressureof 4.5 bar becomes established, this drops to 0.5 bar overnight. Waterand MTBE are added to the reaction mixture, and the phases areseparated. The aqueous phase is extracted with 2×30 ml of MTBE and thecombined organic phase is washed with 40 ml of water and 40 ml ofsaturated NaCl solution. The extract is dried over sodium sulfate andthe solvent is distilled off. Product weight: 90.87 g. The product wasdistilled in vacuo.

T_(bath) T_(head) p ° C. ° C. mbar 50.3 24.1 0.80

3.40 g of the fluoroepoxide from Example 1, 8.94 g of fluoroalcohol(PPOL-1) and 0.36 g of sodium (elemental)

PPOL-1 is initially introduced in a round-bottomed flask. Elementalsodium is added with cooling. For complete dissolution of the sodium,the reaction mixture is heated gently. The reaction mixture issubsequently called again and the epoxide is added. When the addition iscomplete, the reaction mixture is stirred at 80° C. for 20 h. MTBE andwater are added to the reaction mixture and the phases are separated.The aqueous phase was extracted with 2×30 mL of MTBE. The combinedorganic phase is washed with in each case 40 ml of water and 40 ml ofsaturated NaCl solution. The extract is dried over sodium sulfate andthe solvent is distilled off. Product weight: 15.04 g.

The product is distilled in vacuo.

p T_(bath) T_(head) mbar ° C. ° C. 0.80 105.4 78.3

Product weight: 4.7 g

Example 2

The starting materials are combined in a 50 ml pressure reactor andslowly heated to 130° C. After 20 h, the reaction is terminated andwater and MTBE are added to the reaction mixture. The phases areseparated and the aqueous phase is extracted with 2×25 mL of MTBE. Thecombined organic phases is subsequently washed with in each case 30 mlof water and 30 ml of saturated NaCl solution. The extract is dried oversodium sulfate and the solvent is distilled off. The reaction mixture ispurified by distillation. Product weight: 6.55 g

GC MS shows 82.77% of product and 6.81% of isomer.

Example 3

The starting materials are combined in a 50 ml pressure reactor andslowly heated to 130° C. After 20 h, the reaction is terminated andwater and MTBE are added to the reaction mixture. The phases areseparated and the aqueous phase is extracted with 2×25 mL of MTBE. Thecombined organic phases is subsequently washed with in each case 30 mlof water and 30 ml of saturated NaCl solution. The extract is dried oversodium sulfate and the solvent is distilled off.

GC MS shows: 87.82% of product.

Example 4

The starting materials are combined in a 50 ml pressure reactor andslowly heated to 130° C. After 20 h, the reaction is terminated andwater and MTBE are added to the reaction mixture. The organic phaseexhibits an orange coloration. The phases are separated and the aqueousphase is extracted with 2×25 mL of MTBE. The combined organic phases issubsequently washed with in each case 30 ml of water and 30 ml ofsaturated NaCl solution. The extract is dried over sodium sulfate andthe solvent is distilled off. GC MS by means of PCI has a mass peak of488. This peak corresponds to about 50% of the peak areas. Thiscorresponds to the product plus adducted ammonium.

The invention claimed is:
 1. A compound of formula (I′)

where Rf is CF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—, a=1 or 2, b=1, c=0, d=0, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, and, if R is a group Rf′, Rf and Rf′ are different, or of formula (VI′)

where Rf is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, L is a single bond or a divalent organic group, and X is a cationic, amphoteric or anionic group.
 2. A compound of formula (I′)

where Rf is CF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—, a=1 or 2, b=1, c=0, d=0, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, and, if R is a group Rf′, Rf and Rf′ are different.
 3. The compound according to claim 2, wherein Rf is CF₃—(CF₂)—O—.
 4. The compound according to claim 2, wherein R is a C1-C20 alkyl group.
 5. The compound according to claim 2, wherein Rf′ is of the following formula CF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—(CR¹R²)_(e)—(CR³R⁴)_(f)—O_(g)—, where R¹, R², R³ and R⁴, independently of one another, are hydrogen or an alkyl group, a=0, 1, 2 or 3, b=0 or 1, c=0, 1, 2 or 3, d=0 or 1, e=0, 1, 2, 3 or 4, f=0, 1, 2, 3 or 4 and g=0 or
 1. 6. The compound according to claim 2, wherein Rf is CF₃—(CF₂)₂—O—.
 7. The compound according to claim 1, which is a compound of formula (VI′).
 8. The compound according to claim 4, wherein Rf is CF₃—(CF₂)₀₋₃— or CF₃—(CF₂)₀₋₃—O—.
 9. The compound according to claim 7, wherein R is a C1-C20 alkyl group.
 10. The compound according to claim 7, which is a compound of formula (VI′), wherein Rf is CF₃—(CF₂)₀₋₃—O—.
 11. A product selected from the group consisting of paints, coatings, printing inks, protective coatings, special coatings in electronic or optical applications, photoresists, top antireflective coatings or bottom antireflective coatings, developer solutions and wash solutions and photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes, photographic coatings and coatings of optical elements, comprising a compound according to claim
 7. 12. A composition comprising one or more compounds according to claim 7 and a vehicle which is suitable for an application.
 13. The composition according to claim 12, which is selected from the group consisting of paints, coating preparations, fire-extinguishing compositions, lubricants, washing compositions, cleaning compositions, de-icers, developer solutions, wash solutions, photoresists for photolithographic processes, cosmetic products, agrochemicals, floor polishes, hydrophobicising compositions for textile finishing and hydrophobicising compositions for glass treatment.
 14. A compound of formula (VI′)

wherein Rf′ is of the following formula CF₃—(CF₂)_(a)—O_(b)—(CF₂)_(c)—O_(d)—(CR¹R²)_(e)—(CR³R⁴)_(f)—O_(g)—, where R¹, R², R³ and R⁴, independently of one another, are hydrogen or an alkyl group, a=0, 1, 2 or 3, b=0 or 1, c=0, 1, 2 or 3, d=0 or 1, e=0, 1, 2, 3 or 4, f=0, 1, 2, 3 or 4, and g=0 or 1, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, L is a single bond or a divalent organic group, and X is a cationic, non-ionic, amphoteric or anionic group, and, if R is a group Rf′, Rf and Rf′ are different.
 15. A compound of formula (VI′)

wherein Rf is CF₃—(CF₂)₀₋₃—, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, L is a single bond or a divalent organic group and X is a cationic, non-ionic, amphoteric or anionic group and, if R is a group Rf′, Rf and Rf′ are different.
 16. A method for preparing a compound of formula (VI)

where Rf is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, R is a linear or branched alkyl group, optionally containing one or more heteroatoms, or a group Rf′, Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, L is a single bond or a divalent organic group and X is a cationic, non-ionic, amphoteric or anionic group, comprising reacting a compound of formula (I)

where Rf is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms, R is a linear or branched alkyl or siloxane group, optionally containing one or more heteroatoms, or a group Rf′, and Rf′ is a fluorinated, linear or branched alkyl group, optionally containing one or more heteroatoms. 